Water

Very polar Oxygen is highly electronegative H-bond donor and acceptor High b.p., m.p., heat of vaporization, surface tension Properties of water

Water dissolves polar compounds solvation shell

Non-polar substances are insoluble in water Many lipids are amphipathic

Hydrogen Bonding of Water Crystal lattice of ice One H 2 O molecule can associate with 4 other H 2 0 molecules Ice: 4 H-bonds per water molecule Water: 2.3 H-bonds per water molecule

Relative Bond Strengths Bond typeKJ/mole H 3 C-CH 3 88 H-H104 Ionic10-20 H-bond3-6 Hydrophobic interaction1-3 van der Waals1

Biological Hydrogen Bonds   H-Bond distance = ~0.2 nm DNA strands held together by H-bonds

Ionization of Water H H 2 0H 3 O + + OH - K eq = [H + ] [OH - ] [H 2 O] H 2 0 H + + OH - K eq =1.8 X M [H 2 O] = 55.5 M [H 2 O] K eq = [H + ] [OH - ] (1.8 X M)(55.5 M ) = [H + ] [OH - ] 1.0 X M 2 = [H + ] [OH - ] = K w If [H + ]=[OH - ] then [H + ] = 1.0 X 10 -7

pH Scale  Devised by Sorenson (1902)  [H+] can range from 1M and 1 X M  using a log scale simplifies notation  pH = -log [H + ]  Neutral pH = 7.0

Weak Acids and Bases Equilibria Strong acids / bases – disassociate completely Weak acids / bases – disassociate only partially Enzyme activity sensitive to pH weak acid/bases play important role in protein structure/function

Conjugate acid conjugate base pairs HA + H 2 O A - + H 3 O + HA A - + H + HA = Conjugate acid ( donates H + )(Bronstad Acid) A - = Conjugate base (accepts H + )(Bronstad Base) K a = [H + ][A - ] [HA] K a & pK a value describe tendency to loose H + large K a = stronger acid small K a = weaker acid pK a = - log K a

pKa values determined by titration

Phosphate has three ionizable H + and three pKas

Buffers Buffers are aqueous systems that resist changes in pH when small amounts of a strong acid or base are added. A buffered system consist of a weak acid and its conjugate base. The most effective buffering occurs at the region of minimum slope on a titration curve (i.e. around the pKa). Buffers are effective at pHs that are within +/-1 pH unit of the pKa

Henderson-Hasselbach Equation 1) K a = [H + ][A - ] [HA] 2) [H + ] = K a [HA] [A - ] 3) -log[H + ] = -log K a -log [HA] [A - ] 4) -log[H + ] = -log K a +log [A - ] [HA] 5) pH = pK a +log [A - ] [HA] HA = Conjugate acid A - = Conjugate base * H-H equation describes the relationship between pH, pKa and buffer concentration

Case where 10% acetate ion 90% acetic acid pH = pK a + log 10 [0.1 ] ¯¯¯¯¯¯¯¯¯¯ [0.9] pH = (-0.95) pH = 3.81

pH = pK a + log 10 [0.5 ] ¯¯¯¯¯¯¯¯¯¯ [0.5] pH = pH = 4.76 = pK a Case where 50% acetate ion 50% acetic acid

pH = pK a + log 10 [0.9 ] ¯¯¯¯¯¯¯¯¯¯ [0.1] pH = pH = 5.71 Case where 90% acetate ion 10% acetic acid

pH = pK a + log 10 [0.99 ] ¯¯¯¯¯¯¯¯¯¯ [0.01] pH = pH = 6.76 pH = pK a + log 10 [0.01 ] ¯¯¯¯¯¯¯¯¯ [0.99] pH = pH = 2.76 Cases when buffering fails